Abstract
This paper provides data on the occurrence of selected human pharmaceuticals (carbamazepine, clofibric acid, diclofenac, fenofibrate, fenoprofen, gemfibrozil, ibuprofen, ketoprofen, and naproxen) including steroid hormones (17β-estradiol, 17α-ethinylestradiol, and estrone) in influents/effluents to/from the four principal wastewater treatment plants (WWTPs) serving the city of Rome (Italy), in two different sampling campaigns. Target compounds were also analyzed in the receiving River Tiber and River Aniene. Analytical determination was carried out by LC-MS/MS after sample cleanup and concentration by off-line solid-phase extraction (SPE). The aim of the study was to increase the information currently available on the presence and persistence of pharmaceuticals in Italian urban wastewaters and to evaluate the environmental impact of the pharmaceutical residues discharged through effluents into the receiving rivers. Results indicated that after the treatment processes, most of pharmaceuticals were not completely eliminated, as average removal efficiencies were in the 14–100 % wide range during both sampling periods, with higher yields in spring than in winter. Levels detected in overall samples ranged from 5 to 2,230 ng/L in influents and from 5 to 1,424 ng/L in effluents. Carbamazepine, diclofenac, ibuprofen, and gemfibrozil showed the highest persistence to removal. Concentrations in the receiving waters were about one order of magnitude lower than in effluents, with a tendency to increase progressively through the urban tract of the river. Finally, an environmental risk analysis showed that carbamazepine, gemfibrozil, and estrone can pose a high risk at the concentrations detected in effluents and a medium risk in rivers, highlighting their potential hazard for the health of the aquatic ecosystem.
Similar content being viewed by others
References
Al Aukidy M, Verlicchi P, Jelic A, Petrovic M, Barcelò D (2012) Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy. Sci Total Environ 438:15–25
Andreozzi R, Marotta R, Paxèus N (2003) Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment. Chemosphere 50:1319–1330
Bueno MJM, Gómez MJ, Herrera S, Hernando MD, Agüera A, Fernández-Alba AR (2012) Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: two years pilot survey monitoring. Environ Pollut 164:267–273
Calamari D, Zuccato E, Castiglioni S, Bagnati R, Fanelli R (2003) Strategic survey of therapeutic drugs in the Rivers Po and Lambro in Northern Italy. Environ Sci Technol 37:1241–1248
Calza P, Medana C, Padovano E, Giancotti V, Minero C (2013) Fate of selected pharmaceuticals in river waters. Environ Sci Pollut Res 20:2262–2270
Carlsson C, Johansson AK, Alvan G, Bergman K, Kühler T (2006) Are pharmaceuticals potent environmental pollutants? Part I: environmental risk assessments of selected active pharmaceutical ingredients. Sci Total Environ 364:67–87
Castiglioni S, Bagnati R, Calamari D, Fanelli R, Zuccato E (2005) A multiresidue analytical method using solid-phase extraction and high-pressure liquid chromatography tandem mass spectrometry to measure pharmaceuticals of different therapeutic classes in urban wastewaters. J Chrom A 1092:206–215
Castiglioni S, Bagnati R, Fanelli R, Pomati F, Calamari D, Zuccato E (2006) Removal of pharmaceuticals in sewage treatment plants in Italy. Environ Sci Technol 40:357–363
Collado N, Rodriguez-Mozaz S, Gros M, Rubirola A, Barceló D, Comas J (2014) Pharmaceuticals occurrence in a WWTP with significant industrial contribution and its input into the river system. Environ Pollut 185:202–212
De Graaf MS, Vieno NM, Kujawa-Roeleveld K, Zeeman G, Temmink H, Buisman CJN (2011) Fate of hormones and pharmaceuticals during combined anaerobic treatment and nitrogen removal by partial nitritation-anammox in vacuum collected black water. Water Res 45:375–383
Directive 2000/60/EC of the European Parliament and of the Council of October 23 establishing a framework for community action in the field of water policy (FWD), O.J. L 327, December 22, (2000).
Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy, L 226/1 (2013).
Ellis JB (2006) Pharmaceutical and personal care products (PPCPs) in urban receiving waters. Environ Pollut 144:184–189
EMEA (2006) European Medicines Agency Pre-Authorization. Evaluation of medicines for human use. Committee for Medicinal Products for Human Use (CHMP), (Doc. Ref. EMEA/CHMP/SWP/4447/00), 12 pp.
Farmindustria (2013) The association of pharmaceutical companies and member of Confindustria “L’industria farmaceutica in Italia: un’analisi di confronto europeo a partire dai bilanci”. www.farmindustria.it. Accessed 12 April 2014.
Fatta-Kassinos D, Meric S, Nicolaou A (2011) Pharmaceutical residues in environmental waters and wastewater: current state of knowledge and future research. Anal Bioanal Chem 399:251–275
Fent K, Weston AA, Caminada D (2006) Ecotoxicology of human pharmaceuticals. Aquatic Toxicol 76:122–159
Ferrari B, Paxèus N, Lo Giudice R, Pollio A, Garric J (2003) Ecotoxicological impact of pharmaceuticals found in treated wastewaters: study of carbamazepine, clofibric acid, and diclofenac. Ecotoxicol Environ Safety 55:359–370
Ferrari F, Gallipoli A, Balderacchi M, Ulaszewska MM, Capri E, Trevisan M (2011) Exposure of the main Italian river basin to pharmaceuticals. J Toxicol 2011:1–11
Golovko O, Kumar V, Fedorova G, Randak T, Grabic R (2014) Seasonal changes in antibiotics, antidepressants/psychiatric drugs, antihistamines and lipid regulators in a wastewater treatment plant. Chemosphere 111:418–426
Gonzáles-Alonso S, Catalá M, Romo Marota R, Rodríguez Gil JL, Gil de Miguel A, Valcárcel Y (2010) Pollution by psychoactive pharmaceuticals in rivers of Madrid metropolitan area (Spain). Environ Int 36:195–201
Gracia-Lor E, Sancho JV, Serrano R, Hernández F (2012) Occurrence and removal of pharmaceuticals in wastewater treatment plants at the Spanish Mediterranean area of Valencia. Chemosphere 87:453–462
Grenni P, Patrolecco L, Ademollo N, Tolomei A, Barra Caracciolo A (2013) Degradation of gemfibrozil and naproxen in a river water ecosystem. Microchem J 107:158–164
Gros M, Petrović M, Barceló D (2007) Wastewaters treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ebro River basin (Northeast Spain). Environ Toxicol Chem 26(8):1553–1562
Gros M, Petrović M, Ginebreda A, Barceló D (2010) Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environ Int 36:15–26
Gruppo di Lavoro OsMed (2012) L’uso dei farmaci in Italia. Rapporto Nazionale anno 2012, pp. 393. Agenzia Italiana del Farmaco AIFA www.agenziafarmaco.gov.it. Accessed 6 October 2014.
Halling-Sørensen B, Nielsen SN, Lanzky PF, Ingerslev F, Holten Lützhøft HC, Jørgensen SE (1998) Occurrence, fate and effects of pharmaceutical substances in the environment: a review. Chemosphere 36:357–393
Heberer T (2002) Occurrence, fate and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett 131:5–17
Hernando MD, Mezcua M, Fernández-Alba AR, Barceló D (2006) Environmental risk assessment of pharmaceutical residues in wastewater effluents, surface waters and sediments. Talanta 69:334–342
Isidori M, Nardelli A, Pascarella L, Rubino M, Parrella A (2007) Toxic and genotoxic impact of fibrates and their photoproducts on non-target organisms. Environ Int 33(5):635–41
ISTAT (2014) National Institute of Statistics, Population Housing Census, www.dati.istat.it. Accessed 13 October 2014
IUPAC (1999) International Union of Pure and Applied Chemistry. Harmonized guidelines for in-house validation of methods of analysis. Technical Report 1999. http://www.iupac.org/projects/1997/501_8_97.html.
Johnson AC, Belfroid A, Di Corcia A (2000) Estimating steroid oestrogen inputs into activated sludge treatment works and observations on their removal from the effluent. Sci Total Environ 256:163–173
Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002) Pharmaceuticals, hormones and other organic wastewater contaminants in U.S. streams, 1999–2000: a national reconnaissance. Environ Sci Technol 36:1202–1211
Kummerer K (2009) The presence of pharmaceuticals in the environment due to human use—present knowledge and future challenges. J Environ Manage 90:2354–2366
Laganà A, Bacaloni A, De Leva I, Faberi A, Fago G, Marino A (2004) Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in sewage treatment plants and natural waters. Anal Chim Acta 501:79–88
Lin AYC, Yu TH, Lin CF (2008) Pharmaceutical contamination in residential, industrial, and agricultural waste streams: risk to aqueous environments in Taiwan. Chemosphere 74:131–141
Löffler D, Römbke J, Meller M, Ternes TA (2005) Environmental fate of pharmaceuticals in water/sediment systems. Environ Sci Technol 39:5209–5218
Loos R, Gawlik BM, Locoro G, Rimaviciute E, Contini S, Bidoglio G (2009) EU-wide survey of polar organic persistent pollutants in European river waters. Environ Pollut 157:561–568
Loos R, Carvalho R, Comero S, António DC, Ghiani M, Lettieri T, Locoro G, Paracchini B, Tavazzi S, Gawlik BM (2012) EU Wide Monitoring Survey on wastewater treatment plant effluents, Technical Report European Commission, Joint Research Centre, Institute for Environment and Sustainability EUR 25563 EN, doi:10.2788/60663; pp. 138.
Martínez Bueno MJ, Gomez MJ, Herrera S, Hernando MD, Agüera A, Fernández-Alba AR (2012) Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: two years pilot survey monitoring. Environ Pollut 164:267–273
Patrolecco L, Ademollo N, Grenni P, Tolomei A, Barra Caracciolo A, Capri S (2013) Simultaneous determination of human pharmaceuticals in water samples by solid phase extraction and HPLC with UV-fluorescence detection. Microchem J 107:165–171
Quinn B, Gagné F, Blaise C (2008) The effects of pharmaceuticals on the regeneration of the cnidarian, Hydra attenuata. Sci Total Environ 402:62–69
Repice C, Dal Grande M, Maggi R, Pedrazzani R (2013) Licit and illicit drugs in a wastewater treatment plant in Verona, Italy. Sci Total Environ 463–464:27–34
Santos JL, Aparicio I, Alonso E (2007) Occurrence and risk assessment of pharmaceutically active compounds in wastwater treatment plants. A case study: Seville city (Spain). Environ Int 33:596–601
Spongberg WJ, Acuña J, Vargas J, Murillo M, Umaña G, Gómez E, Perez G (2011) Reconnaissance of selected PPCP compounds in Costa Rica surface waters. Water Res 45:6709–6717
Stuer-Lauridsen F, Birkved M, Hansen LP, Holten Lützhøft HC, Halling-Sørensen B (2000) Environmental risk assessment of human pharmaceuticals in Denmark after normal therapeutic use. Chemosphere 40:783–793
Tauxe-Wuersch A, De Alencastro LF, Grandjean D, Tarradellas J (2005) Occurrence of several acidic drugs in sewage treatment plants in Switzerland and risk assessment. Water Res 39:1761–1772
TDG (1996) Technical Guidance Document in support of Council Directive 93/67/EEC on risk assessment for new notified substances and Commission Regulation (EC) 1488/94 on risk assessment for existing substances. Office for Official Publications of the European Communities, Luxembourg
Ternes TA, Joss A (2006) Human pharmaceuticals, hormones and fragrances. The challenge of micropollutants in urban water management. IWA Publishing, London, pp 243–277
Tixier C, Singer HP, Oellers S, Müller SR (2003) Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen and naproxen in surface waters. Environ Sci Technol 37:1061–1068
Valcárcel Y, Gonzáles Alonso S, Rodríguez-Gil JL, Castaño A, Montero JC, Criado- Álvarez JJ, Mirón IJ, Catalá M (2013) Seasonal variation of pharmaceutically active compounds in surface (Tagus River) and tap water (Central Spain). Environ Sci Poll Res 20(3):1396–1412
Verlicchi P, Al Aukidy M, Zambello E (2012) Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after a secondary treatment: a review. Sci Total Environ 429:123–155
Verlicchi P, Al Aukidy M, Jelic A, Petrović M, Barceló D (2014) Comparison of measured and predicted concentrations of selected pharmaceuticals in wastewater and surface water: a case study of a catchment area in the Po valley (Italy). Sci Tot Environ 470–471:844–854
Vieno NM, Tuhkanen T, Kronberg L (2005) Seasonal variation in the occurrence of pharmaceuticals in effluents from a sewage treatment plant and in recipient water. Environ Sci Technol 39:8220–8226
Vieno NM, Tuhkanen T, Kronberg L (2007) Elimination of pharmaceuticals in sewage treatment plants in Finland. Water Res 41(5):1001–1012
Yu Y, Wu LS, Chang AC (2013) Seasonal variation of endocrine disrupting compounds, pharmaceuticals and personal care products in wastewater treatment plants. Sci Total Environ 442:310–316
Zhang Y, Geiben SU, Gal C (2008) Carbamazepine and diclofenac: removal in wastewater treatment plants and occurrence in water bodies. Chemosphere 73:1151–1161
Zuccato E, Castiglioni S, Bagnati R, Melis M, Fanelli R (2010) Source, occurrence and fate of antibiotics in the Italian aquatic environment. J Hazard Mater 179:1042–1048
Acknowledgments
The authors wish to acknowledge the ACEA S.p.A. Group for providing wastewater samples and information about the treatment plants monitored. The authors express gratitude to Dr. Stefano Polesello (IRSA-CNR) for his constructive comments on the manuscript.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Leif Kronberg
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(DOCX 23 kb)
Rights and permissions
About this article
Cite this article
Patrolecco, L., Capri, S. & Ademollo, N. Occurrence of selected pharmaceuticals in the principal sewage treatment plants in Rome (Italy) and in the receiving surface waters. Environ Sci Pollut Res 22, 5864–5876 (2015). https://doi.org/10.1007/s11356-014-3765-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-014-3765-z